Metalliferous water-insoluble azo-dye-



, thoxychlorophenyl,

United States Patent 3,121,073 METALLHERGUS WATER-INSQLUBLE AZO-IEYE-STUFFS AND PRQCEEES 1 0R PREPG HEM Hasso Hertel, Reinhard Mohr, andWaiter Sinai), all of Ofienbach (Main), Germany, assignors to FarbwerkeHoechst Aktiengesellsehaft vormals Meister Lucius & Briining, Frankfurtam Main, Germany, a corporation of Germany No Drawing. Filed Jan. 9,1962, er. No. 165,213 Claims priority, application Germany Jan. 12, B616 Claims. (Cl. 260-446) The present invention relates to valuable newmetalliferous water-insoluble azo-dyestuffs and to a process forpreparing them, in particular it relates to complex metal compounds ofwater-insoluble azo-dyestufi s having the general formula selected fromthe group consisting of wherein A represents a member of the groupconsisting of phenyl, methylphenyl, methoxyphenyl, ethoxyphenyl,chlorophenyl, nitrophenyl, methylchlorophenyl, memethylnitrophenyl,methoxynitrophenyl, dichlorophenyl, methylsulfonyluitrophenyl,acetylphenyl, chlorophenoxy-chlorophenyl, benzoylamino-dimethoxyphenyl,naphthyl, quinolyl, indazolyl, methyl-benzimidazolyl,methylchloro-benzimidazolyl and 5 oxide-Z-carbonylamino,

3,121,073 Patented Feb. 11, 1964 methyl, ethyl, methoxy and ethoxy, Zrepresents a member of the group consisting of 2.3-hydroxynaphthoylamino, 6-bromo-2.3-hydroxynaphtholyamino, Z-hydroxyanthracene 3carbonylamino, 3 hydroxydiphenylene 2-hydroxycarbazole-3-carbonylaminoand S-hydroxy-1.2,l'.2'-benzocarbazole-4-carbonylamino, and X representsa member of the group consisting of phenyl, methylphenyl, methoxyphenyl,ethoxyphenyl, chlorophenyl, nitrophenyl, dimethyl- 10 phenyl,dimethoxyphenyl, methylmethoxyphenyl, methylchlorophenyl,methoxychlorophenyl, dimethoxychlorophenyl, naphthyl andmethoxydiphenylene oxide radical.

Water-insoluble azo-dyestuifs produced by coupling on the fiber yieldingblack dyeings are much appreciated in the dyeing industry, since theygenerally permit to produce very intense dyeings possessing good generalproperties of fastness. Vat dyestuiis, sulfur dyestuffs and substantivedyestuffs do not yield black dyeings having a high depth of color.

Among the coupling components used in the ice color industry for theproduction of black dyeings on cellulose fibers the 2.3-hydroxynaphthoicacid arylamides have particular importance, since on account of theiraffinity they can be well fixed on the fiber and, due to the variousdegrees of this afiinity, they are suitable for all common dyeingmethods and apparatuses. Apart from the dyeings on the basis of4.4'-diamino-diphenylamine which have a low intensity and possess amoderate fastness to light and a poor fastness to chlorine, the diazocomponents used in practice belong to the series of the aminoazocompounds which yield dyeings of a good fastness to washing and tochlorine and a medium fastness to light. There are especially used thediazonium salts of 4-nitro-4-amino-2.S-dimethoxy-l.l-azo-benzene, of 4'-(4" aminophenylamino) 4-amino-2-ethoxy-5-methyl- 1.1'-azobenzene, of1-(2'-ethoxyphenyl-1'-azo)-4-amino naphthalene and other products. Allthese compounds yield intense dyeings which, however, do not exceed amedium fastness to light and which tend to bleeding in 40 the peroxidebleach test and in boiling-off with caustic dine and the highlysubstantive ortho-hydroxycarboxylic acid arylamides of benzo-carbazolepossess a very good fastness to light. In practice, however, it isgenerally impossible to attain a complete coupling of the couplingcomponent on the fiber so that by treating the material in boilingalkaline solutions and bleaching it with peroxide, white material isstained in undesired yellowish to reddish brown tints.

In spite of a good selection of available components it has hitherto notbeen possible to produce, under phenylimino-dihydrotriazolyl, Rrepresents a member of economically acceptable conditions, intense blackdyeings the group consisting of hydrogen and methyl, R and R representmembers of the group consisting of hydrogen,

which satisfy the high requirements as to fastness to light and show agood resistance in the peroxide bleach test.

3 We have found that new metalliferous water-insoluble azo-dyestuffs areobtained by coupling in substance, on the fiber or on another substratuma diazonium compound of an amine having the general formula N NH inwhich A represents an aromatic or heterocyclic radical, R represents ahydrogen atom or an alkyl group and R and R represent hydrogen atoms,alkyl or alkoxy groups, with an arylamide of an aromatic or heterocyclicortho-hydroxy carboxylic acid or of an acylacetic acid, the componentsbeing selected so that they are free from groups imparting solubility inwater such, for example, as sulfonic acid or carboxylic acid groups, andtreating the dyestuff so obtained with an agent yielding metal.

The treatment of the water-insoluble azo-dyestufis obtainable by thepresent invention with the agents yielding metal may be carried out byknown methods during or after the coupling substance or on the fiber.When the dyestuffs are produced on the fiber, the metallizationmay beconducted by adding the compound yielding metal to the developing bathor already to the impregnation bath. The treatment of the dyestuffs withthe agents yielding metal after the coupling, may be carried out in asecond bath which is neutral, weakly alkaline or weakly acid. The bathmay contain dispersing agents or detengents, for example, a fattyalcohol polyglycol ether, an alkyl phenol polyglycol ether, analkylnaphthol polyglycol ether, a fatty acid polyglycol ester or a fattyacid amide polyglycol ether.

As agents yielding metal there are preferably used for the process ofthe present invention compounds yielding copper, cobalt, nickel, ironand zinc which may be inorganic or organic salts of these metals such,for example, as chlorides, bromides, sulfates, nitrates, formates oracetates, or complex compounds of these metals, especially withhydroxy-alkylamines such, for example, as diethanolamine,triethanolamine or N-methyl-ethanolamine, or with amino-carboxy licacids such, for example, as aminoaceti'c acid or nitrilotriacetic acid,or with aliphatic hydroxy-carboxylic acids such, for example, astartaric acid, citric acid or igluconic acid, or with alkali metalphosphates such, for example, as alkali metal polyphosphates or alkalimetal pyrophosphates. When an agent yielding cobalt is used, theaddition of an oxidizing agent such, for example, as an alkali metalperborate, an alkali metal percarbonate or a compound of hexavalentchromium has a favorable effect on the metallization.

By dyeing or printing according to the ice color method there areproduced on vegetable fibers, including fibers of regenerated cellulosemainly black dyein gs which possess good general fastness properties andespecially a very good fastness to light.

The dyestuffs may be produced on vegetable fibers at a longgoodsto-liquor ratio. Piece goods, warps and ribbons may be dyed in acontinuous manner or printed by the base or naphtholate printingprocesses.

The novel dyestuffs can also be produced on animal fibers, such as woolor silk by the dyeing methods commonly applied to these fibers.

The dyestuffs can also 'be prepared in substance and converted into thecomplex metal compoundsby treating them with an agent yielding metal.The complex metal compounds so obtained are suitable for dyeingsynthetic fibers and also for coloring organic plastic masses of highmolecular weight. As coupling components there are used in the processthe present invention the arylarnides of aromatic or heterocyclicortho-hydroxycanboxylic acids or of acylacetic acids such, for example,as the 'arylam-ides of 2.3-hydroxynaphthoic acid or the derivativesthereof substituted in 6- position, or arylamides ofZ-hydroxyanthracene-3-carboxylic acid, 3-hydroxy-diphenyleneoxide-Z-carboxylic acid, 2-hydroxycarbaZole-3-carboxylic acid,5-hydroxy-l.2.1.2'- benZocarbazole-4-canboxylic acid, acetylacetic acid,ben- Zoylacetic acid or terephthaloyl-bis-acetic acid. 'The arylamideradical may belong to the benzene, naphthalene, diphenyl or diphenyleneoxide series.

As amino compounds which correspond to the aforesaid general formulafand may advantageously be used in the process of the present invention,there are mentioned 7 compounds in which the aromatic or heterocyclicradical A may be substituted by groups which do not impart solubility inwater, for example halogen atoms, al-kyl, alkoxy, aryloxy,trifiuoromethyl, nitro, alkylsulfone, arylsul-fone, acyl, iacylarnino,sulfonic acid amide or canbox-ylic acid amide groups which may containsubstituents, furthermore cyano, arylazo or dialkylamino groups. Thepreparation of these compounds may be conducted, for example, bycoupling the diazoni-urn compounds of aromatic or heterocyclic amineswith 7-aminobenzimidazoles of the general formula in whichR R and R havethe meanings indicated above.

but they are not intended to limit it thereto, the parts being by Weightunless otherwise stated and the relationship of 7 parts by Weight toparts *by volume being the same as that of the kilogram to the liter.

EXAMPLE 1 Cotton yarn was treated for 45 minutes at 35 C., at agoods-to-liquor ratio of 1:20, in an impregnation bath, prepared asdescribed below, centrifuged and thendeveloped, first for 10 minutes at20 C. and then, after being slovv-ly heated to to C., for 20 to 30minutes at 90 to 95 C. in a developing bath prepared as describedibelow. Subsequently, the yarn was rinsed and soaped first for 15minutes at 60 C., then for 15 minutes at 95 C. with a solutioncontaining per liter of water jl gram of a reaction product from about10 mols of ethylene oxide and 1 mol of nonylphenol and 3 grams of sodiumcarbonate, rinsed again and dried.

1m pregnation Bath 4.5 grams of l-(2.3'-hydroxynaphthoylamino)-2 .4 di-'methoxy-S chlorobenzene were dissolved in cc. of denatured ethylalcohol, 1.5 cc. of sodium hydroxide sol u-j tion of 38 B6, 4.5 cc. ofhot water and 1.5 cc. of formaldehyde solution of 33% strength. Thesolution so'oba tained Was made up to 1 liter with water at 35 C.containing 3 grams of a condensation product from fatty acids of highmolecular Weight and protein degradation products and 10 cc. of sodiumhydroxide solution of 30 B.

Developing Bath 2.7 grams of 7-amino-5-methyl-4-(3'-methy1phenyl-1 azo)-benzimidazole were diazotized with 6 cc. of hydrochlori'c acid of 20 B.and 4 cc. of sodium nitrite solution 1:5 and the diazo solution soobtained was introduced into a bath containing .per liter of water 2grams of a reaction product from about 20 mols of ethylene oxide and 1mol of octadecyl alcohol, '20 grams of sodium acetate and 2.8 gramsofnickel sulfate.

A black dyeing having a good fastness to light and to wet processing wasobtained.

EXAMPLE 2 Cotton yarn was treated for 45 minutes at 35 C., at agoods-to-liquor ratio of 1:20 in an impregnation bath prepared asdescribed below, centrifuged and developed for 30 minutes at 20 C. inthe developing bath prepared as described below. The yarn was thenrinsed and metallization was conducted in the following manner:

2.8 grams of nickel sulfate dissolved in 28 cc. of water were mixed with30 cc. of a solution of aminoacetic acid in water (1:10) and made up to1 liter with a solution containing 1 gram of a reaction product fromabout mols of ethylene oxide and 1 mol of nonylpheuol, 3 grams of sodiumcarbonate and water. The dyed material was after-treated in thissolution at a goods-to-liquor ratio of 1:20, by heating from 60 to 95 C.and by treating the material for 30 minutes at 95 C. The yarn was thensoaped for minutes at 95 C. with a solution containing per liter ofwater 1 gram of a reaction product from about 10 mols of ethylene oxideand 1 mol of nonylphenol, and 3 grams of sodium carbonate, rinsed anddried.

Impregnation Bath 1.75 grams of2-(2'.3-hydroxynaphthoylamino)-naphthalene were dissolved in 3.5 cc. ofdenatured ethyl alcohol, 0.9 cc. of sodium hydroxide solution of 38 B.,1.8 cc. of hot water and 0.9 cc. of formaldehyde solution of 33%strength. The solution so obtained was made up to 1 liter with water at35 C. containing 3 grams of a condensation product from fatty acids ofhigh molecular Weight and protein degradation products and 10 cc. ofsodium hydroxide solution of 38 B.

Developing Bath 3.3 grams of7-amino-5-methy1-4-(2-methoxy-5-nitrophenyl-1'-azo)-benzimidazole werediazotized with 6 cc. of hydrochloric acid of 20 B., 18 cc. of aceticacid and 4 cc. of sodium nitrite solution 1:5 and the diazo solution soobtained was introduced into a bath containing per 1 liter of water 2grams of .a reaction product from about 20 mols of ethylene oxide and 1mol of octadecyl alcohol and 20 grams of sodium acetate.

A black dyeing having a good fastness to light and to wet processing wasobtained.

EXAMPLE 3 42 parts of 7-amino-5-methyl-4(2'-methoxyphenyl-1'-azo)-benzimidazole were pasted up with 120 parts by volume of aceticacid. After the addition of 45 parts by volume of concentratedhydrochloric acid the mixture was cooled to 0 C. and diazotized byadding 10.5 parts of sodium nitrite in the form of a concentratedaqueous solution and then rapidly heating to to C. The mixture wasdiluted with water to obtain about 1000 parts by volume. The diazosolution so obtained was added dropwise, while stirring well, to asolution of 2.3-hydroxynaphthoylarninobenzene prepared as follows: 30.5parts of 2.3-hydroxynaphthoylaminobenzene were dissolved in parts byvolume of alcohol and parts by volume of 5 N-sodium hydroxide solution,and a solution containing in 3000 parts by volume of water 200 parts ofsodium carbonate was added. When the coupling was complete, a solutionof 19 parts of copper sulfate and parts by volume of triethanola-mine in300 parts by volume of water was introduced. Subsequently, the mixturewas heated to C. and treated for two hours at this temperature. Thecomplex copper compound of the dyestuff so obtained was filtered off,washed and dried. It was a dark powder.

In the following table further components are listed which can be usedin the process of the invention, and also the tints produced by formingthe metalliferous azo-dyestuffs from these components on the fiber,which likewise possess good properties of fastness.

Tint

Diazo component Coupling component Copper Cobalt Nickel complex complexcomplex 7-amino-5-methy1-4-(2'-methoxyphenyl-1-azo)-2.B-hydroxynaphthoyl-aminoben ene black black black.

benzimidazole.

D0 1-(2.3-hydroxynaphthoylammo)-3-n1trobendo do Do.

Z8118. Do 4.4-bis-(2. -hydroxynaphthoylamino)-3.3- brown b1aek blackbrownblack brown.

dimethoxydiphenyl. Dn 1-(3-hydroxydiphenylene-oxide-2'-earbonylamgreygrey grey.

ino)-2.5-dimethoxy-benzene. Do 1-(2hydroxycarbazole-3-carbonylamino)-4-black black black.

chlorobenzene. Do 1-(2-hydroxyanthracene-3-car'bonylamino)-2- blackolive. greenish grey black olive.

methylbenzene. Dn 1-(5-hydroxy-1.2-1.2-benzoearbazole-4-carblack blackblack.

bonylarnino)-4-methoxybenzene. Dn1-(5-hydroxy-l.2-1.2-benzocarbazole-4-car- -do do Do.

bonylamino) 2-methyl-imethoxybenzene. Do4Agiis-afetoacetylamino-3.3"dimethyldidull violet dark browndark brown.

p any D0 terephthaloyl-bis-(l-acetylamino-Zkdimethoxyblue black.-."brownish black brown.

5-ehlorobe11zene) black. Do 1-(3-l1ydroxydiphenylene oxide-2'-carbonylblue grey grey brownish grey.

amino)-naphthalene. Dn 1-(3-hydroxydiphenylene oxide-2-carbony1- grey doDo.

amino)-2-ethoxybenzene. Do terephthaloyl-bis-(1-acetylamino-2-methoxy-4-reddish black black brownblack brown.

chloro-fi-methylbenzene) Do 2-2.cetoacetylamino-fi-ethoxybenzthiazolegrey b1ue greenish blueblue. Dol-acetoacetylainino-2.5-dimethoxy+chl0robencurrant reddish blue--reddish blue.

zene. Do l-acetoacetylamino-Z.fi dimethy n ene do Do.7-amino-5-methyl-4-(2-methyl-5-chlorophenyl-2.3-hydroxynaphthoylaminobenzene black black black.

1-azo)-benzimidazole.

Do 2-(2.3-hydroxynaphthoylammo)-nap -r1n -do Do. Do1-(2.3'-hydrownaphthoylamino)-2.fi-diinethoxydo do Do.

i-chlorobenzene.

Tint

Diazo component Coupling component Copper Cobalt Nickel complex complexcomplex Famine-2.fi-dimethyl--phenylazobenzimidazol1-(2.BJnydroxynaphthoy1amino)-4-chlorobenblack black black.

ZQHQ. Do 1-(2.3-hydroxynaphthoylamino)-2.5-dimethdo "do Do.

oxy-4-chlorobenzene. 7-a1ni110-2.fi-dirnethyl-i-(3'-chl0r0pheny1-1-azo)-1-(2.3hydroxynaphthoylamino)naphthalene.. do -do D0.

benzimidazole.

Do 1-(2l3-hydroxynaphthoylamino)-2-metboxy-4- do d Do.

chloro--metl1ylbenzcne.

2. The complex nickel compound of the water-in- We claim: solubleazo-dyestuft having the formula 1. The complex metal compounds selectedfrom the group consisting of nickel, copper and cobalt compounds (1)0113E of water-insoluble azo-dyestuffs having a formula selected T T Y Yfrom the group consisting of I I N02 N\ /NE OH CO-NH- 1?; f: OH

A-N=N N=NZ-X 3. The complex nickel compound of the Water-insolubleazo-dyesturf having the formula N NE OCH: CH3

R3 R2 R2 R; I I l AN=N-- N %l N=N N=NA N\ /NE OH HO- HN\ /N a i lowerlower alkoxy alkoxy whereinArepresents a member of the group consistingof 4. The complex nickel compound of the water-insolphenyl,methylphenyl, methoxyphenyl, ethoxyphenyl, uble azo-dyestufi having theformula chlorophenyl, nitrophenyl, methylchlorophenyl,methoxychlorophenyl, niethylnitrophenyl, methoxynitrophenyl, OCHS ([3133dichlorophenyl, methylsulionylnitrophenyl, acetylphenyl,chlorophenoxy-chlorophenyl, benzoylamino-dimethoxy- 5O :NQNZN phenyl,naphthyl, quinolyl, indazolyl, methylbenzimidazolyl,methylchloro-benzimidazoiyl and phenylimino-di hydrotriazolyl, Rrepresents a member of the group consisting of hydrogen and methyl, Rand R represents members of the group consisting of hydrogen, methyl, 5.The complex nickel compound of the water-insoluethyl, methoxy andethoxy, Z represents a member of ble azo-dyestufi having the formulaOCHa $113 N NH ()3 3o-NH O00H= 0 01 the group consisting of2.3-hydroxynaphthoylamino, 6- T116 comPlex PP compound of theWater-11180111- bromo-2.3-hydroxynaphthoylamino, 2 hydroxyanthrablealo-dyesfllfi having the la cene-3-carbonylamino, 3-hydroxydiphenyleneoxide-2- carbonylamino, Z-hydroxycarbazole 3 carbonylamino (3H3 andS-hydroxy-1.2.1'.2'-benzocarbazole-4-carbonylamino,

and X represents a member of the group consisting of phenyl,methylphenyl, methoxyphenyl, ethoxyphenyl, I I chlorophenyl,nitrophenyl, dimethylphenyl, dimethoxy- C1 NH OH CO"NH phenyl,methylmethoxyphcnyl, methylchlorophenyl, me- 4 thoxychlorophenyl,dimethoxychlorophenyl, naphthyl and methoxydiphenylene oxide radical. 7No references cited.

1. THE COMPLEX METAL COMPOUNDS SELECTED FROM THE GROUP CONSISTING OFNICKEL, COPPER AND COBALT COMPOUNDS OF WATER-INSOLUBLE AZO-DYESTUFFSHAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF